3-azo derivatives of 1-substituted 2, 5-diketo-7-methylpyrimidopyrazoles



Patented Sept. 25, 1951 UNITED STATES 3-AZO DERIVATIVES OF I-SUBSTITUTED 2,5- DIKETO-7- METHYLPYRIMIDOPYRA- ZOLES No'Drawing. Application July 9, 1948, Serial No. 37,974

6 Claims.

The present invention relates-to 3-azo derivatives of 1-substituted-2,5-diketo-7-methylpyrimidopyrazoles wherein the radical joined to said pyrimidopyrazoles by the azo group is the residue of a diazotizable amine of the aromatic or heterocyclic series.

It is an object of the present. invention to provide 3-azo derivatives of 1substituted-2,5-diketo- '7-methylpyrimidopyrazoles useful as filter and anti-halation dyes in photographic film and as colorforme-rs in producingid e images by color forming development.

Other objects will be apparent from the following specification in which the preferred details and embodiments are described.

The azo compoundsof this invention are characterized byv a structure corresponding to the general formula:

Ha ltn, l.

wherein R is alkyl, e. g.,- methyl, ethyl, propyl, butyl, octyl, decyl, dodecyl, myristyl, tetradecyl, stearyl, octadecyl, etc.; aryl, e. g., phenyl, naphthyl, diphenyl and the like; aralkyl, e.- g., benzyl, methylbenzyl, ethylbenzyl and the like; heterocyclic, e. g., benzothiazolyl, a-quinolyl, a-DYIidYl and the like; R1 represents a substituted or unsubstituted aryl group of thebenzene, naphthalene, anthrace-ne, and phenanthrene series; or a heterocyclic group, e. g., pyrrole, pyrazole, pyrazclone, carbazole, primuline, etc., with or without \vater-solubilizing groups such as sulfonic acid or 'carboxylic acid groups; and n represents 1 or 2. Said alkyl, aryl, aralkyl, and-heterocyclic groups designated by the value. B may be substituted bya halogen such as chlorine, bromine, or. iodine, aminov groups, e. g., primary amino, secondary-amino, such as methyl'amine, phenylamine, and the like, or a tertiary amine, such as dimethylamine, diphenylamine, 'etc., sulfonamino, orsolublizing groups such as sulfonic or carboxylic acid groups.

The azo compounds illustrated by the foregoing general. formula are obtained by coupling any diazotized amine of the type common in azo dye chemistry, with a l-substituted-2,5-diketo- '7-methylpyrimidopyrazole of the general "for- -mula:

o=o o cm H( .7\ /N\ N 47113 {I wherein R. is of the same value as above.

The 1 substituted-2,5-diketo-7-methylpyrim idopyrazoles characterized by the foregoin for-.

mula are prepared. according to the method described in application Serial No.. 563,974, filed; on November 17, 1944, now.United States Patent? 2,481,466, issued September 6, 1949. In general, the method consists of heating 1 mol of a3- amino-5-pyrazolone, the' l-position of which! is substituted by a radical represented by R above," with '1 to. 1' /2': mols of diketene in the presence of a solvent-diluent, suchlas,ifon.texample, an aro-r.

matic hydrocarbon, or anoxygenated hydrocarbon, i. e. an ether, ketone, or alcohol, at a tem-: perature ranging from C. to 130 C; from 2 Instead of employing a solvent-(lib? to 5 hours.

uent for the reaction, the reactants may be sus:

pendedin water and-the aqueous suspension heated at a temperature ranging from 80 C. to

C. for the same period of time.

In preparing the azo derivatives, the above 1 substituted-2,5-diketo 'iemethylpyrimidopyraq zoles are coupled with a 'diazonium salt in the usual manner. Any primary aromatic or hetero cyclic amine capable of undergoing the diazotization reaction may be employed infthe preparation of the diazoniumsalt. As examples of illustrative amines, the following may be mentioned:

Aniline p-Chloroaniline 2,5-dichloroaniline p-Hydroxyaniline a-Naphthylam-ine p-Nitroaniline o-Nitroaniline 3-nitro-4-to1uidine- 2-nitro-4-chloroaniline 2,4-dinitroaniline Sulfanilic acid 1-amino-2-naphthol sulfonic acid p-Aminodiphenylamine Benzidine ATENT fo FFic-E f 4,4'-diamlnostilbene A mixture of 0.6 gram of o-anisidine, 10 cc.

1-naphthylamine-fi-sulfonic acid of water, 20 grams of ice, and 5 cc. of hydro- 1-(phenyl-4sulfo)-3-methyl-4-amino-5-pyrazchloric acid (6 N) was diazotized with a soluolone tion of 0.4 gram of sodium nitrite in 5 cc. of

a-Naphthylamine 5 water. The resulting o-anisidine diazonium Aniline-2,5-disulfonic acid chloride solution was added to a solution of 1.2

1-naphthylamine-7-sulfonic acid grams of l-phenyl-2,5-diketo-7-methylpyrimido- 2-chloro-4-aminobenzoic acid pyrazole in cc. of methanol followed by 9 cc.

Benzidine-2,2'-disulfonic acid of sodium hydroxide solution (6 N). The reac- 2-amino-4-sulfobenzoic acid 10 tion mixture Which separated, was filtered and Primuline Washed with water to yield the azo dye. An

2,6-diaminotoluene-4-sulfonic acid alcoholic solution of this dye is yellow.

3-aminobenzoic acid When the 1-phenyl-2,5-diketo7-methylpyrim- 2-amino-8-naphthol-3fi-disulfonic acid idopyrazole is coupled with diazotized sulianilic 1,4-diaminonaphtha1ene-3-5u1fonic id acid, an alkali-soluble yellow dyestufi is obtained.

Dianisidine j Tondine EXAMPLE II m'mhdme 1 (p-tolyl) -2,5-dilteto-3- (p-methylphenylazo) p-Amimbenzyl'ifiethylamme 7-methylpyrimidopyrazole p-Acetaminoamline N Anthranilic acid o,o'-Diaminodiphenic acid l;

2,2'-diaminocarbazol 3,3'-dichlorobenzidine 2-nitrobenzidine Hi 4,4-diaminostilbene-2,2'-disulfonic acid 4,4'-diamino-2,2'-tetramethyltriphenylmethane Z-aminobenzothiazole Z-amino-6-ethoxybenzothiazole H Z-aminobenzoxazole a 4-amino-5-pyrazolone 1 pheny1 3wailing 4 amino 5 pyrazolone A mixture of 0.6 gram of p-toluldine, 10 cc,-

1 pheny1 3 amino 5 pyrazolone of watei, 20 grams of ice, and 5 cc. of hydro- 4,4-diaminodiphenylurea-3,3-disulfonic acid 0.1110116 acid (6 N) was q i q i 4,4,diammodmhenmmethane tion of 0.4 gram of sod um nitrite in 5 cc of 2 (4, pheny1ammo) fi methylbenzothiazole water. The resulting diazonium salt solution baminonerimidinefidisuuonic acid. was added to a solution of 1.4 grams of l-(ptolyl) -2,5-diketo-7-methylpyrimidopyrazole in 30 The azo compounds, in view of the1r ketocc. of methanol. After the addition of 8 cc. of methylene configuration, may have the strucsodium hydroxide (6 N), the reaction mixture ture of a hydrazone or some other tautomeric separated out. The dyestuff dissolves in organic form or a mixture of these as indicated by the solvents such as ethyl alcohol to yield'a yellow following partial structures: solution.

C=NNH R1 CHN=N R1 C-N=N- R 0= =0 OH l 1E1 N I l R 11 1'1 11 R It is to be understood that I intend to include EXAMPLE III within the scope of my invention any of these modifications or forms in which the azo compounds of the present invention may exist. It is to be further noted that regardless of the form N S in which they may exist, their utility as filter s and anti-halation dyes and as color formers for 0:0 (IJ-CHN=N C producing dye images by color forming developat N (3:0

ment is not diminished or impaired. N

The following examples illustrate the prepara- E tion of the azo compounds of the present invenf tion.

EXAMPLE I O l'phenyl'z5'diketo'3'(o'methmyphenylazo) A mixture of 1.9 grams of 2-amino-6-ethoxy- 1 (a-quinolyl) -2,5-diketo-3- (6-ethomybenzothiazoZe-Z-azo) -7-methylpyrimidopyrazole fimethyzpymmzdopwazoze benzothiazole, 50 cc. of water, 50 grams of ice,

N OCH: and 15 cc. of hydrochloric acid (6 N) was diazo- V I tized with a solution of 0.7 gram of sodium nitrite v in 5 cc. of water. The resulting diazonium salt 5 N solution was added to a solution of 3.1 grams of p v 0 1 (a-quinolyl) 2,5 diketo 7 methylpyrimil l dopyrazole in 50 cc. of methanol followed by 8 cc. of sodium hydroxide (6 N). The resulting mixture became orange in color and the product was filtered, washed with water, and purified by recrystallization from methanol.

z t-sacre- "EXAMPLE IV -p,p r-"Bis (3:-azo-1 ,7'-dimeth=yl -2 5-diketopyrimidopyrazolefistilbe-ne I 2 o=c fe -cH N=NOoH=oH+@N=N-nc c o=0 tm 3 fi l (2:0 I 0=t /N\ JH j .s "7 6H; CH: on, on,

A mixture of 1.2 grams of 4,4'-diamino stilbene, I claim: 25 cc. of water, 30 grams of ice, and 10 cc. of 1. A dyestuffs having the general formula: hydrochloric acid (6 N) was diazotized with a N solution of 0.7 gram of sodium nitrite in 5 cc. 0 CH R of water. The resulting diazonium salt solution methyl-2,5-diketopyrimidopyrazole in 40 cc. of methanol followed by 10 cc. of sodium hydroxide (6 N). The resulting mixture became deep orange in color and the product was filtered, washed with Water, and purified by recrystallization from methanol.

=0 was added to a solution of 1.0 gram of 1,7-di- N =0 ls J be. t wherein R is selected from the class consisting of alkyl of not more than 18 carbon atoms, aryl ofthe benzene, naphthalene, and diphenylene series, aralkyl of the benzene series, and mono- EXAMPLE v unsubstituted nitrogenous heterocyclic group selected from the class consisting of benzothiazol l Y, fi' gg 3 f g gg g a-QulllOlYl, and u-pyridyl, R1 represents the radiy 1711mm 0 e cal of a diazotizable amine and n is a numeral ranging from 1 to 2.

. Example I was repeated with the exception that 1 gram of 1-methyl-2,5-diketo-7-methylpyrimidopyrazole was substituted for 1.2 grams of 1 phenyl-2,5-diketo-7-methylpyrimidopyrazole. An alcoholic solution of this dye is yellow. The azo dye having the formula:

The azo compounds of the present invention are useful in many photographic applications. The dyes, both water-soluble and Water-insolu- C ble, may be used in the silver dye bleach process m N 5:0 of color photography wherein dye images are formed by the selective destruction of the dyes (EH in the presence of silver images. They may also be used as filter and anti-halation dyes in lightsensitive photographic film.

The azo compounds, since they contain an azo substituent in the reactive coupling position of H the pyrimidopyrazole nucleus, will react in color a I forming development with the oxidation prod- 4. The azo dye having the formula:

uct of the developer in the usual manner to form 5 colored images. The azo group of the pyrimido- OC'Hi pyrazoles is displaced by the aryl-amino group during dye image formation. A I l While I have disclosed the preferred embodi- H ments of my invention and the preferred modes 0 N of carrying the same into effect, it will be readily I 5 apparent to those skilled in the art that many N variations may be made therein without departing from the spirit thereof. Accordingly, the O scope of my invention is to be limited solely by the following claims. 5. The azo dye having the formula:

o=( \(|3(FHN=NOCH=CHON=NHZ(F% HG N o=o o= N on on; on. on. $11.

6. The azo dye having the formula:

OCH;

REFERENCES CITED 5 UNITED STATES PATENTS Number Name Date 2,403,329 Bavley July 2, 1946 2,427,911 Kendall et al Sept. 23, 1947 2,459,226 Kendall et a1 J an. 18, 1949 2,481,466 Bavley Sept. 6, 1949 

2. THE AZO DYE HAVING THE FORMULA: 